CA1258597A - Photopolymerizable photosensitive composition - Google Patents
Photopolymerizable photosensitive compositionInfo
- Publication number
- CA1258597A CA1258597A CA000438783A CA438783A CA1258597A CA 1258597 A CA1258597 A CA 1258597A CA 000438783 A CA000438783 A CA 000438783A CA 438783 A CA438783 A CA 438783A CA 1258597 A CA1258597 A CA 1258597A
- Authority
- CA
- Canada
- Prior art keywords
- photopolymerizable
- photosensitive composition
- ethylenically unsaturated
- group
- photopolymerizable photosensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/111—Polymer of unsaturated acid or ester
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
TITLE OF THE INVENTION
PHOTOPOLYMERIZABLE PHOTOSENSITIVE COMPOSITION
ABSTRACT OF THE DISCLOSURE
A photopolymerizable photosensitive composition character-ized by comprising a photopolyrmerizable photosensitive resin having polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof, and a photopolymerization initiator.
PHOTOPOLYMERIZABLE PHOTOSENSITIVE COMPOSITION
ABSTRACT OF THE DISCLOSURE
A photopolymerizable photosensitive composition character-ized by comprising a photopolyrmerizable photosensitive resin having polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof, and a photopolymerization initiator.
Description
'J
`~ 1;2585~3~7
`~ 1;2585~3~7
2 --BACXGROUND OF THE INVENTION
- -- 1. Field of the Invention This invention relates to photopolymerizable photo-sensitive compositlons which comprise, as main components, photopolymerizable photosensitive resins having ethylenically unsaturated groups of the specific type in the side chains or end groups thereof, and photopolymerization initiators. More particularly, it - relates to photosensitlve compositions which comprise novel resins of high sensitivity.
2. Descr;ption of the Prior Art - Photopolymerizable photosensitive compositions have now ~een used in the printing industry as photosensitive resin plates for relief printing and offset PS (pre-sensitized) plates. In particular, the offset PS
plates are much simpler in handling than known wipe-on plates, contri~uting to save the steps of the printing plate-making process. Accordingly, the PS plates have recently become popular more and more and are extending their market rapidly. Most of currently sold PS plates make use of so-called diaz~-type photosensitive materials typical of which is a condensation product of paradiazodiphenylamine and formaldehyde. The PS plates using this type of diazo compound have relatively good l~S~359~
.
sensitivity but are disadvantageous in that they are poor in printing durability, chemical resistance, and storage stability. In contrast, compositions comprising photo-crosslinkable photosensitive resins are able to form network molecular bonds therein upon irradiation of light, giving a printing plate of good printing durability. ~owever, the compositions have the drawback that, in most cases, organic solvents are used as a developer to remove the photosensitive resin composition in non-crosslinked areas, thus being - ~ unfavorable from the standpoint of wor~ing environment and that the running cost becomes high. In contrast, with composltions comprising photopolymerizable photo-sensitive resins, the development is feasible with use of aqueous solutions and particularly aqueous alkali solutions. The aqueo~s solutions are more~inexpensive than organic solvents coupled with another advantage in that they are less dangerous particularly from the physiological standpoint. In addition, the photo-polymerizable photosensitive-resin compositions form a molecular structure of three-dimensional network in portions where exposed, so that the resulting printing plate is very advantageous from the standpoint of printing durability.
Other important fields of applications of photocross-linkable and photopolymerizable photosensitive resin _~ f~
l;~SB597 compositions include plating materials for metal corrosion at the time of fabrication of printed circuits, mask or resist materials for soldering processes, resist materials for chemical milling of metals, and resist materials used for fabrication of multi-layer metallic lithographs and gravure plates. For instance, in the fabrication of printed circuits, a substrate for the circuit, e.g. a copper-substrate, is covered with a photosensitive resin composition on the surface thereof and exposed to light in an imagewise pattern, after which non-exposed areas are completely removed by the use of a suitable liquid developer while leaving a substantial area of- the substrate to be exposed to air.
The portions from which the photosensitive resin 1~ composition has been removed are etched by any known technique or plated with a metal. In these fields of applications, an aqueous alkali solution which is less dangerous can be used as a liquid developer, and photopolymerizable photosensitive compositions from which a durable resist film can be obtained are very advantageous.
In the above-mentioned various fields, a new image exposure system is being introduced in order to improve the working efficiency. For example, in case where an 25 image is formed on an offset PS plate or a substrate for printed circuit, it is the common practice to bring . ., 6~ ~
` i~S8597 5 _ an oriyinal film into intimate contact with the PS
plate or substrate under which ~ight is irradiated on - the photosensitive layer of the plate or substrate through the film. In particular, with some offset PS plates, a system of exposure of the plate by an enlarged projection through a microfilm has been put into practice. This system has the advantage over known systems in that silver halide films can be saved.
Also, another system is put into practice in which visible light from a laser ~eam, e.g. an argon ion - laser beam, is directly scanned or exposed on a photo-sensitive layer of the substrate, thereby forming an image. This system does not need fabrication of silver halide films at all, so that much labor can ~e saved.
i5 Moreover, a further advancement of computerization will permit diIe~t petIieval of signals of an image original from a computer. Thus, this type of laser exposure system is helieved to be promising. However, in order to effectively form an image using the above-discussed new exposure systems, photosensitive resin compositions which are covered on individual substrates are required to have higher photosensitivity. It is generally accepted th~t photopolymerizable photosensitive resin compositions are superior to aiazo photosensitive materials and photocrosslinkable photosensitive resin compositions. However, the above requirement is not adequately satisfied.
l~S8597 Accordingly, an object of the present invention is to provide compositions comprising photopolymerizable - - resins which can be developed by the use of aqueous alkali solutions and have higher speed of photo-sensitivity.
~nown photopolymerizable photosensitive resins are, for example: proaucts obtained by addition reaction of glycidyl (meth-)acrylates with polymers having carboxyl groups in the side chains thereof such as, for example, - (co-)polymers (meanlng the same as resins) of (meth-)-acrylic acid, maleic acid and the like; products obtained by addition reaction of (meth-)acrylic acid with polymers having epoxy groups in the side chains such as, for example, glycidyl (meth-)acrylate (co-Tpolymers or epoxy-novolak resins; products obtained by reaction of (meth-)acrylic chloride with polymers having hydroxyl groups in the side chains thereof such as, for example, hydroxyethyl (meth-)-acrylate (co-)polymers, vinyl alcohol and the like thereby introducing ~meth-) acryloyl groups thereinto;
and products obtained by reaction between polyurethanes obtained by polycondensation of polyols and diiso-cyanates, and (meth-)acrylates having hydroxyl groups.
Thus, polymers having monofunctional ethylenically unsaturated groups in the side chains thereof are conventionally used.
i;~58S97 The increase in amount of the ethylenically unsaturated compound in the composition containing photopolymerizable photosensitive resin usually results in an increase of the sensitivity.
However, ethylenically unsaturated compounds are ordinarily viscous liquids at a normal temperature. If the compound is added in an amount sufficient to obtain a desired level of sensitivity, the photosensitiv~ layer becomes fairly adhesive on the surface thereof, making - the handling very difficult.
` SUM~ARY` OF- '1'11~ INVENTION
The present inventor have made intensive studies~~n order to solve the problems or di~ficulties of the prior art.
As a result, it has been found that when resins having a specific type of ethylenically unsaturated group in the side chains or end groups thereof are used, there can be obtained photopolymerizable photosensitive resin compositions which have excellent photosensitivity without lowerings of developability and image quality. The present invention is based on the above finding.
The prominent feature of the present invention resides in a photopolymerizable photosensitive composition which is characterized by comprising a photopolymerizable photo- ~
sensitive resin having polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof and a photopolymerization initiator.
DETAILED DESCRIPTION OF ~E PREFERRED EMBODIMENTS
The present invention is described in detail.
The photopol~merizable photosensitive r~sins useful in the present invention should have polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof. The ethylenically unsaturated groups should be two or more in num~er per one side chain or end group.
When the photopolymerizable photosensitive composltions are irradiated with actinic light, the resins having polyfunctional ethylenically unsaturated groups are exerted with the direct action of photodecomposed products of a photopolymerization initiator which is another essential component as will be described hereinafter, and are also synergistically exerted with the action of photo-decomposed products of an ethylenically unsaturated compound attacked by the photodecomposed products of the photo-polymerization initiator. As a result, the resin undergoes the three-dimensional addition polymerization together with the ethylenically unsaturated compound and -is thus efficiently cured and substantially insolubilized, thereby forming an image area.
lZSBS~7 _ 9 _ In prior art, when a photo-cured image is formed using monofunctional resins, it has been essential to incorporate ethylenically unsaturated compounds in photopolymerizable photosensitive compositions.
In contrast, when the resin of the invention having poly-functional ethylenically unsaturated groups is used, it was unexpectedly found that good photocured images are formed without using ethylenically unsaturated compounds in combination.
The polyfunctional ethyienically unsaturated groups have, for example, a structural unit of the following general formula o - -C(R )m ((R O ~ CR -CH2)n (in which Rl represents a hydrogen atom, an alkyl group such as methyl, ethyl or the like, and a hydroxyalkyl group such as hydroxymethyl, hydroxyethyl or the like, R2 represents an alkylene group such as methylene~ ethylene, trimethylene or the like, R3 represents hydrogen atom or methyl, m is 0 or 1 and n is 2 or 3 provided that m + n = 3, and p is an integer of 1 to 3).
The polyfunctional ethylenically groups having a structural unit of the above formula wherein R2 is methylene group and . p is 1 are preferred~
- lZS8597 The photopolymeri~able photosensitive resins of the present invention are, for example, resins having structural units of the following general formula -(CH-CR4)-R COO--~CH2 ~ C(R )m--~R O ~ CR =CH2]n (in which Rl, R2, R3, m, n and p have the same meanings as defined above, respectively, R4 represents hydrogen atom or methyl group, R5 represents hydrogen atom or carboxyl group, and q is an integer of 0 to 3).
Such resins can readily be obtained by the esterification between polymers having carboxylic or carboxylic anhydride groups in the side chains or end groups and polyfunctional ethylenically unsaturated compounds having hydroxyl groups by any known method. ~ -The polymers having carboxylic acid or carboxylic anhydride groups in the side chains or end groups include, forexample, tmeth-lacrylic acid homopolymers, (meth-~acrylic acid/(meth-)acrylate copolymers, styrene/(meth-)acrylic acld copolymers, styrene/maleic anhydride copolymers, and partially esterified products thereof.
These (co)polymers deteriorate in developability when the molecular weight is excessively large. On the contrary, when the molecular weight is too small, the sensitivity and the strength of a photocured image portion lower.
1~ 5~ 5~ ~
Accordingly, an average molecular weight of the (co)polymers is preferred to be in the range of 1,000 - 50,000 and most preferably in the range of 2,000 - 10,000.
Specific examples of the polyfunctional ethylenically unsaturated compounds include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dimethylol-methanol diacrylate (glycerol-1,3 -diacrylate), dimethylol-methanol dimethacrylate (glycerol 1,3-dimethacrylate), trimethylolmethane diacrylate, trimethylolmethane dimethacrylate, and the like.
The reaction between the polymers and the polyfunctional ethylenically unsaturated compounds is an ordinarily known esterification reaction between carboxylic acids and alcohols. For instance, ethers or aromatic hydrocarbons are used as solvents for the reaction and the reaction mixture is heated in the presence of a catalyst such as sulfuric acid, paratoluenesulfonic acid or the like. With carboxylic anhydrides, products esterified with unsaturated compounds having hydroxyl groups can be readily obtained by merely heating them in solvents of aromatic hydrocarbons.
Also, there is mentioned a method in which carboxylic acids are converted into carboxylic chlorides by the use of thionyl chloride or the like, and then reacted with unsaturated . ~ ~ 9 lZS8~;~7 compounds having hydroxyl groups in the presence of an alkali catalyst such as pyridine, triethanolamine or the like. In order to suppress occurrence of the addition polymerization of polyfunctional ethylenically unsaturated compounds, it is preferable to aad reducible compound to the reaction system as a polymerization inhibitor. As such a compound, hydroquinone is effective.
When the ratio of the introduction of the polyfunctional ethylenically unsaturated groups into the polymer in the side chains thereof is increased, the sensitivity increases but the developability with aqueous alkali solutions lowers.
Although the amount of the polyfunctional ethylenically unsaturated compound may vary depending on the type of polymer or liquid developer, it is convenient to add the polyfunctional ethylenically unsaturated compound to the polymer in the side chains thereof in an amount of 0.03 -0.98 equivalent, preferably 0.10 - 0.80 equivalent, to the carboxyl groups of the polymer.
The photopolymerizable photosensitive resins of the present invention may be used in combination with other polymers.
Polymers being admixed are used in an amount of 5 - 500 parts by weight per 100 parts by weight of the photopolymer-izable photosensitive resin.
Examples of the polymers being admixed include (meth-)acrylic acia homo-polymers or copolymers of (meth-)acrylic ester with other (meth-)acrylic esters, vinyl compounds including, L-~ ~.
lZS85~7 for example, vinyl ether, vinyl acetate or saponified 2 products thereof, styrene, vinylpyrolidone, butadiene and so on; copolymers of polyacrylic anhydride, maleic acid, maleic semi-ester, semi-amide and~or derivatives of anhydride or itaconic acid with suitable comonomers such as styrene, ethylene, vinyl ether, vinyl acetate and the like; cellulose derivative or the like.
It is preferable to add ethylenically unsaturated compounds to the photopolymerizable photosensitive composition in order to improve the sensitivity.
' Such compound is a monomer havinq ethylenically unsaturated double bonds which is attacked, when the photopolymerizable photosensitive resin composition is irradiated with actinic light, by the photodecomposed product of the photopolymeriza-tion initiator, and is addition-polymerized three-dimensionally together with the polyfunctional resin and cured, rendering the composition substantially insoluble.
The term "monomer" used herein is intended to mean a concept relative to polymer material and include oligomers such as dimers, trimers and the like, aside from monomers in a strict sense.
The monomers having ethylenically unsaturated double bonds include, for example, unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and - 1~58597 aromatic polyhydroxy compounds, and esters obtained by esterification reaction of unsaturated carboxylic acids, polycarboxylic acids and polyhydroxy compounds such as the above-indicated aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds and the like.
Specific examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.
The aliphatic polyhydroxy compounds include, for example, - 10 dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, propylene glycol, 1,2-butanediol and the like, trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerol and the like, tetrahydric or L5 polyhydric alcohols such as pentaerythritol, tripentaery-thritol and the like, and polyhydroxycarboxylic acids such as dihydroxylmaleic acid and the like.
The aromatic polyhydroxy compounds include hydroquinone, resorcin, catechol, pyrogallol and the like.
Examples of the polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acia, pyromellitic acid, benzophenonedi-carboxylic acid, maleic acid, fumaric acid, malonic acid, glutaric acid, adipic acid, sebacic acid, tetrahydro-phthalic acid, and the like.
1~2S8S9~
Examples of the esters of the aliphatic polyhydroxy compounds ana the unsaturated carboxylic acids are acrylates such as ethylene glycol aiacrylate, triethylene glycol diacrylate, tetramethylene glycol aiacrylate, S trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaery-thritol hexaacrylate, tripentaerythritol octaacrylate, glycerol aiacrylate and the li~e; methacrylates such as - triethylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythr-itol tetraacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, ethylene glycol dimethacrylate, 1,2-butanediol dimethacrylate, sorbitol tetramethacrylate and the like; itaconates such as ethylene glycol diitaconate, propylene glycol diitaconate, 1,2-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol tri- -itaconate and the like; crotonates such as ethylene glycol dicrotonate, diethylene glycol dicrotonate, pentaerythritol tetracrotonate and the like; and malates such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and the like.
The esters of the aromatic polyhydroxy compounds and the unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like.
The esters obtained by the esterification reaction of unsaturated car~oxylic acids, polycarboxylic acids and polyhydroxy compounds are not necessarily a single product.
Typical of the esters are indicated in Table 1. In the table, Z represents an acryloyl or methacryloyl group.
., . - : .
lZ585~7 Table 1 .. . .
z--oC2H4--ooC-c6H4 COO C2H4 ~ 2H4~200C~CH2~4cOO~c2H40~2z Z~C2H4~3OC--CH=CH COO~C2 4 3 ~ 2 4~200C ~ COO~C2H40)2Z
- ' ~
2~ C~ C2H5 C
Z--OCH2 ' CH200C--c6H4--cooc~2~ CH2--Z
Z--OCH2;~ ~ 2 Z
- .CH-OOC-CH=CH-COO-CH ~
Z-OCH2~ 2 Z
z--OC2H4--ooC--c6H4--coo C2H4 Z-OCH2 ~ ~ 2 Z
Z-cH2 /c-cH2ooc-c6H4-coocH2-c -CH20-Z
HO--CH2 . - CH2--OH -Z--OCH2 ~ ~ CH2--Z
10 Z-OCH2--C--CH200C--CH=CH--COOCH2--C--CH20--Z
Z--OC2H4--00C~CH2~4Coo ~CH2 Z--OC2H4--00c~cH2~4CoO--CH
Z--OC2H4--00C~CH2~4Coo CH2 ;~
~'~S~S97 Examples of other compounds having ethylenically - unsaturated double bonds used in the present invention include acrylamides such as acrylamide, ethylene bisacrylamide, hexamethylene bisacrylamide and the like;
methacrylamides such as ethylene bismethacrylamide, hexamethylene bismethacrylamide and the like; allyl esters such as diallyl phthalate, diallyl malonate, diallyl fumarate, triallyl isocyanurate and the like; and vinyl-containing compounds such as divinyl adipate, divinyl phthalate, ethylene glycol dlvinyl ether and the like.
Especially, trimethylolpropane triacrylate; trimethylolethane triacrylate, and pentaerythritol tetraacrylate exhibit relatively high sensitivity and are favorable because they do not lower the ink receptivity on the photocured image areas. - `
The photopolymerization ïnitiators which are another essential component of the composition according to the invention are conventionally known initiators. For - instance, benzoin, benzoin alkyl ethers, benzophenone, anthraquinone, benzil, Michler's ketone, and a mixture of biimidazole and Michler's ketone are favorably used.
In order for effective photosensitization by exposure to visible light of an argon ion laser beam, compounding ; systems such as biimidazole and dialkylaminostyryl derivatives, S-triazine and cyanine derivatives, and S-triazine and thiapyrylium derivatives are preferred.
lZS8597 The composition of the present invention comprises the components in the following ratios ranging 10 - 80 wt~, preferably 20 - 60 wt~ of a polymer containing a poly-functional resin, 90 - 20 wt~, preferably 80 - 40 wt% of an ethylenically unsaturated compound, and 0.1 - 20 wt%, preferably 1 - 10 wt% of a photopolymerization initiator.
The photopolymerizable composition of the invention may be further admixed with other ingredients, depending on the purpose, in order IO modify physical properties. For instance, thermal polymerization inhibitors, antioxidants, colorants, plasticizers, application aids and the ike may:
be compounded in an amount not more than 20 wt~ based on the total weight of the three components.
The photopolymerizable composition of the invention may be used to form a photosensitive material in the absence of solvent, or may be dissolved in a solvent to obtain a solu-tion, followed by applyins it on a support, and drying to form a photosensitive material. The solvents are, for example, methyl ethyl ketone, acetone, cyclohexanone, ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, toluene, xylene, benzene, monochlorobenzene, chloroform, carbon ~etrachloride, trichloroethylene, trichloroethane, dimethylformamide, methyl CELLOSOLVE (trademark), ethyl CELLOSOLVE, butyl CELLOSOLVE, tetrahydrofuran, pentoxone(4-methyl-4-methoxy-2-pentanone), methanol, ethanol, propanol and the like.
`, 4`~ X~
The supports applied for preparing a photosensitive material from the photopolymerizable composition of the invention include, for example, sheets of metals such as aluminium, magnesium, copper, zinc, chromium, nickel, iron S and the like or alloys comprising the metals as a main component, papers such as high quality paper, art paper, release paper and the like, inorganic sheets such as glasses, ceramics and the like, and sheets of polymers such as polyethylene tetrephthalate, polyethylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymers, polystyrene, 6-nylon, 6,6-nylon, cellulose diacetate, cellulose triacetate, cellulose acetate butylate, and the like.
These supports may be ap~lied to a photosensitive layer on both sides of the layer. Moreover, the supports may be treated on the surface thereof in order to control the adhesion strength.
In order to prevent the photopolymerizable composition of the present invention from suffering disadvantageous effects of oxygen such as lowered sensitivity, deteriora-tion of storage stability and the like, any known techniques may be used, for example, a releasable transparent cover sheet may be provided on the photosensitive layer, or a covering layer of, for example, a wax material or a water-soluble or an alkali-soluble polymer may be formed on the layer.
12S859~7 The light sources for exposure suitably applicable to the composition of the present invention include general-purpose light source capable of emitting ultraviolet and visible light rays having wavelengths over 180 nm such as, for example, high pressure mercury lamps, xenone lamps, metal halide lamps, fluorescent lamps, tungsten lamps, argon ion laser, helium cadmium laser, krypton laser and the like.
The photopolymerizable composition of the present invention has uses in various fields of, for example, making of printing plates for lithograph, intaglio, and relief printing or the li~e, photoresists for the preparation of :
printed circuits or IC circuits, dry films, non-silver halide lith films, and image formation of relief images and reproduction of images. Having generally described the lS invention, a more complete understanding can be obtained by-refexence to certain specific examples, which are included for purposes of illustration only and are not intended to be limiting unless otherwise specified.
Reference 1 9.0 g of methyl methacrylate, 0.86 g of methacrylic acid (charging ratio by mole = 9/1), and 50 mg of benzoyl peroxide were dissolved in 50 g of dioxane, followed by heating the solution at 80C for 4 hours with agitation while purging with nitrogen and subsequently charging into a large amount of water. The resulting polymer was dissolved in a small amount of acetone and dropped into a - large amount of a methanol/water mixture for re-precipita-i~58597 tion, followed by drying in vacuo to obtain methyl meth-acrylate/methacrylic acid copolymer (molecular weight ~
;, 000) Reference 2 8.08 g (0.01 mole) of a partially esterified product of styrene-maleic anhydride copolymer (styrite C~-2L, molecular weight ~ 5vO00/product by Sankyo Kasei Co., Ltd.), 2.32 g (0.02 mole) of 2-hydroxyethyl acrylate, and 20 mg of hydroquinone were dissolved in 50 g of dioxane, followed by heating at 100C for 4 hours under agitation and dropping in a large amount of water for precipitation. Thereafter, the precipitate was dried in vacuo to obtain a carboxylic acid semi-ester polymer (monofunctional resin).
Re~erence 3 The procedure of Reference 2 was repeated except that pentaerythritol triacryla~e was used instead of 2-hydro-xyethyl acrylate, there~y obtaining a carooxylic semi-ester polymer (polyfunctional resin).
Reference 4 The procedure of Reference 2 was repeated except that trimethylolethane diacrylate was used instead of 2-- - hydroxyethyl acrylate, therehy obtaining a carboxylic acid semi-ester polymer (polyfunctional resin).
Example 1 0.45 g of a partially esterified product of styrene/maleic anhydride copolymer (STYRITE CM-2L, trademark, product of Sankyo Kasei l'~S859~7 Co., Ltd.), 0.1 g of the methyl methacrylate/methacrylic acid copolymer prepared in Reference 3, 0.45 g of the polyfunctional resin of reference 3, 0.5 g of trimethylol-propane triacrylate (product of Osaka Organic Chem. Ind.
Co., Ltd.), each 0.04 g of photopolymerization initiators represented ~y the following structural formulas ~I] and [II~, and 0.012 g of "~ictoria Pure Blue BOH" (product of ~odogaya Chemical Co., Ltd.)-were dissolved in 18 g of ethyl cellosolve. The resulting photosensitive solution was applied onto a grained and anodized al~minium plate by the use of a whirler in a dry thickness of 20 mg/dm2. At this stage no stic~ness was observed on the photosensitive layer. Thereafter, an aqueous polyvinyl alcohol solution was applied onto the photosensitive layer to form a protective layer with a dry thickness of 20 mg/dm2, thereby o~taining a sample A step tablet (by Eastman Kodak Co.) was deposited on the sample under vacuum, followed by expos-ing it to light from a 3 KW high pressure mercury lamp (U~IPULSE UMH-3000, trademark, by Ushio Electric Inc.) at a distance of 1 m for 15 seconds and developing with a liquid developer consisting of an aqueous 1% sodium silicate solu-tion. As a result, the sensitivity (steps of photocured image) was found to be 12 steps. Furthermore, the developa-bility (developing speed, removability by dissolution, and the like), resolution and ink receptivity were found to be good. Thus, the fundamental requirements as the offset PS
plate were satisfied.
i~
125~37 - ~4 -
- -- 1. Field of the Invention This invention relates to photopolymerizable photo-sensitive compositlons which comprise, as main components, photopolymerizable photosensitive resins having ethylenically unsaturated groups of the specific type in the side chains or end groups thereof, and photopolymerization initiators. More particularly, it - relates to photosensitlve compositions which comprise novel resins of high sensitivity.
2. Descr;ption of the Prior Art - Photopolymerizable photosensitive compositions have now ~een used in the printing industry as photosensitive resin plates for relief printing and offset PS (pre-sensitized) plates. In particular, the offset PS
plates are much simpler in handling than known wipe-on plates, contri~uting to save the steps of the printing plate-making process. Accordingly, the PS plates have recently become popular more and more and are extending their market rapidly. Most of currently sold PS plates make use of so-called diaz~-type photosensitive materials typical of which is a condensation product of paradiazodiphenylamine and formaldehyde. The PS plates using this type of diazo compound have relatively good l~S~359~
.
sensitivity but are disadvantageous in that they are poor in printing durability, chemical resistance, and storage stability. In contrast, compositions comprising photo-crosslinkable photosensitive resins are able to form network molecular bonds therein upon irradiation of light, giving a printing plate of good printing durability. ~owever, the compositions have the drawback that, in most cases, organic solvents are used as a developer to remove the photosensitive resin composition in non-crosslinked areas, thus being - ~ unfavorable from the standpoint of wor~ing environment and that the running cost becomes high. In contrast, with composltions comprising photopolymerizable photo-sensitive resins, the development is feasible with use of aqueous solutions and particularly aqueous alkali solutions. The aqueo~s solutions are more~inexpensive than organic solvents coupled with another advantage in that they are less dangerous particularly from the physiological standpoint. In addition, the photo-polymerizable photosensitive-resin compositions form a molecular structure of three-dimensional network in portions where exposed, so that the resulting printing plate is very advantageous from the standpoint of printing durability.
Other important fields of applications of photocross-linkable and photopolymerizable photosensitive resin _~ f~
l;~SB597 compositions include plating materials for metal corrosion at the time of fabrication of printed circuits, mask or resist materials for soldering processes, resist materials for chemical milling of metals, and resist materials used for fabrication of multi-layer metallic lithographs and gravure plates. For instance, in the fabrication of printed circuits, a substrate for the circuit, e.g. a copper-substrate, is covered with a photosensitive resin composition on the surface thereof and exposed to light in an imagewise pattern, after which non-exposed areas are completely removed by the use of a suitable liquid developer while leaving a substantial area of- the substrate to be exposed to air.
The portions from which the photosensitive resin 1~ composition has been removed are etched by any known technique or plated with a metal. In these fields of applications, an aqueous alkali solution which is less dangerous can be used as a liquid developer, and photopolymerizable photosensitive compositions from which a durable resist film can be obtained are very advantageous.
In the above-mentioned various fields, a new image exposure system is being introduced in order to improve the working efficiency. For example, in case where an 25 image is formed on an offset PS plate or a substrate for printed circuit, it is the common practice to bring . ., 6~ ~
` i~S8597 5 _ an oriyinal film into intimate contact with the PS
plate or substrate under which ~ight is irradiated on - the photosensitive layer of the plate or substrate through the film. In particular, with some offset PS plates, a system of exposure of the plate by an enlarged projection through a microfilm has been put into practice. This system has the advantage over known systems in that silver halide films can be saved.
Also, another system is put into practice in which visible light from a laser ~eam, e.g. an argon ion - laser beam, is directly scanned or exposed on a photo-sensitive layer of the substrate, thereby forming an image. This system does not need fabrication of silver halide films at all, so that much labor can ~e saved.
i5 Moreover, a further advancement of computerization will permit diIe~t petIieval of signals of an image original from a computer. Thus, this type of laser exposure system is helieved to be promising. However, in order to effectively form an image using the above-discussed new exposure systems, photosensitive resin compositions which are covered on individual substrates are required to have higher photosensitivity. It is generally accepted th~t photopolymerizable photosensitive resin compositions are superior to aiazo photosensitive materials and photocrosslinkable photosensitive resin compositions. However, the above requirement is not adequately satisfied.
l~S8597 Accordingly, an object of the present invention is to provide compositions comprising photopolymerizable - - resins which can be developed by the use of aqueous alkali solutions and have higher speed of photo-sensitivity.
~nown photopolymerizable photosensitive resins are, for example: proaucts obtained by addition reaction of glycidyl (meth-)acrylates with polymers having carboxyl groups in the side chains thereof such as, for example, - (co-)polymers (meanlng the same as resins) of (meth-)-acrylic acid, maleic acid and the like; products obtained by addition reaction of (meth-)acrylic acid with polymers having epoxy groups in the side chains such as, for example, glycidyl (meth-)acrylate (co-Tpolymers or epoxy-novolak resins; products obtained by reaction of (meth-)acrylic chloride with polymers having hydroxyl groups in the side chains thereof such as, for example, hydroxyethyl (meth-)-acrylate (co-)polymers, vinyl alcohol and the like thereby introducing ~meth-) acryloyl groups thereinto;
and products obtained by reaction between polyurethanes obtained by polycondensation of polyols and diiso-cyanates, and (meth-)acrylates having hydroxyl groups.
Thus, polymers having monofunctional ethylenically unsaturated groups in the side chains thereof are conventionally used.
i;~58S97 The increase in amount of the ethylenically unsaturated compound in the composition containing photopolymerizable photosensitive resin usually results in an increase of the sensitivity.
However, ethylenically unsaturated compounds are ordinarily viscous liquids at a normal temperature. If the compound is added in an amount sufficient to obtain a desired level of sensitivity, the photosensitiv~ layer becomes fairly adhesive on the surface thereof, making - the handling very difficult.
` SUM~ARY` OF- '1'11~ INVENTION
The present inventor have made intensive studies~~n order to solve the problems or di~ficulties of the prior art.
As a result, it has been found that when resins having a specific type of ethylenically unsaturated group in the side chains or end groups thereof are used, there can be obtained photopolymerizable photosensitive resin compositions which have excellent photosensitivity without lowerings of developability and image quality. The present invention is based on the above finding.
The prominent feature of the present invention resides in a photopolymerizable photosensitive composition which is characterized by comprising a photopolymerizable photo- ~
sensitive resin having polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof and a photopolymerization initiator.
DETAILED DESCRIPTION OF ~E PREFERRED EMBODIMENTS
The present invention is described in detail.
The photopol~merizable photosensitive r~sins useful in the present invention should have polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof. The ethylenically unsaturated groups should be two or more in num~er per one side chain or end group.
When the photopolymerizable photosensitive composltions are irradiated with actinic light, the resins having polyfunctional ethylenically unsaturated groups are exerted with the direct action of photodecomposed products of a photopolymerization initiator which is another essential component as will be described hereinafter, and are also synergistically exerted with the action of photo-decomposed products of an ethylenically unsaturated compound attacked by the photodecomposed products of the photo-polymerization initiator. As a result, the resin undergoes the three-dimensional addition polymerization together with the ethylenically unsaturated compound and -is thus efficiently cured and substantially insolubilized, thereby forming an image area.
lZSBS~7 _ 9 _ In prior art, when a photo-cured image is formed using monofunctional resins, it has been essential to incorporate ethylenically unsaturated compounds in photopolymerizable photosensitive compositions.
In contrast, when the resin of the invention having poly-functional ethylenically unsaturated groups is used, it was unexpectedly found that good photocured images are formed without using ethylenically unsaturated compounds in combination.
The polyfunctional ethyienically unsaturated groups have, for example, a structural unit of the following general formula o - -C(R )m ((R O ~ CR -CH2)n (in which Rl represents a hydrogen atom, an alkyl group such as methyl, ethyl or the like, and a hydroxyalkyl group such as hydroxymethyl, hydroxyethyl or the like, R2 represents an alkylene group such as methylene~ ethylene, trimethylene or the like, R3 represents hydrogen atom or methyl, m is 0 or 1 and n is 2 or 3 provided that m + n = 3, and p is an integer of 1 to 3).
The polyfunctional ethylenically groups having a structural unit of the above formula wherein R2 is methylene group and . p is 1 are preferred~
- lZS8597 The photopolymeri~able photosensitive resins of the present invention are, for example, resins having structural units of the following general formula -(CH-CR4)-R COO--~CH2 ~ C(R )m--~R O ~ CR =CH2]n (in which Rl, R2, R3, m, n and p have the same meanings as defined above, respectively, R4 represents hydrogen atom or methyl group, R5 represents hydrogen atom or carboxyl group, and q is an integer of 0 to 3).
Such resins can readily be obtained by the esterification between polymers having carboxylic or carboxylic anhydride groups in the side chains or end groups and polyfunctional ethylenically unsaturated compounds having hydroxyl groups by any known method. ~ -The polymers having carboxylic acid or carboxylic anhydride groups in the side chains or end groups include, forexample, tmeth-lacrylic acid homopolymers, (meth-~acrylic acid/(meth-)acrylate copolymers, styrene/(meth-)acrylic acld copolymers, styrene/maleic anhydride copolymers, and partially esterified products thereof.
These (co)polymers deteriorate in developability when the molecular weight is excessively large. On the contrary, when the molecular weight is too small, the sensitivity and the strength of a photocured image portion lower.
1~ 5~ 5~ ~
Accordingly, an average molecular weight of the (co)polymers is preferred to be in the range of 1,000 - 50,000 and most preferably in the range of 2,000 - 10,000.
Specific examples of the polyfunctional ethylenically unsaturated compounds include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dimethylol-methanol diacrylate (glycerol-1,3 -diacrylate), dimethylol-methanol dimethacrylate (glycerol 1,3-dimethacrylate), trimethylolmethane diacrylate, trimethylolmethane dimethacrylate, and the like.
The reaction between the polymers and the polyfunctional ethylenically unsaturated compounds is an ordinarily known esterification reaction between carboxylic acids and alcohols. For instance, ethers or aromatic hydrocarbons are used as solvents for the reaction and the reaction mixture is heated in the presence of a catalyst such as sulfuric acid, paratoluenesulfonic acid or the like. With carboxylic anhydrides, products esterified with unsaturated compounds having hydroxyl groups can be readily obtained by merely heating them in solvents of aromatic hydrocarbons.
Also, there is mentioned a method in which carboxylic acids are converted into carboxylic chlorides by the use of thionyl chloride or the like, and then reacted with unsaturated . ~ ~ 9 lZS8~;~7 compounds having hydroxyl groups in the presence of an alkali catalyst such as pyridine, triethanolamine or the like. In order to suppress occurrence of the addition polymerization of polyfunctional ethylenically unsaturated compounds, it is preferable to aad reducible compound to the reaction system as a polymerization inhibitor. As such a compound, hydroquinone is effective.
When the ratio of the introduction of the polyfunctional ethylenically unsaturated groups into the polymer in the side chains thereof is increased, the sensitivity increases but the developability with aqueous alkali solutions lowers.
Although the amount of the polyfunctional ethylenically unsaturated compound may vary depending on the type of polymer or liquid developer, it is convenient to add the polyfunctional ethylenically unsaturated compound to the polymer in the side chains thereof in an amount of 0.03 -0.98 equivalent, preferably 0.10 - 0.80 equivalent, to the carboxyl groups of the polymer.
The photopolymerizable photosensitive resins of the present invention may be used in combination with other polymers.
Polymers being admixed are used in an amount of 5 - 500 parts by weight per 100 parts by weight of the photopolymer-izable photosensitive resin.
Examples of the polymers being admixed include (meth-)acrylic acia homo-polymers or copolymers of (meth-)acrylic ester with other (meth-)acrylic esters, vinyl compounds including, L-~ ~.
lZS85~7 for example, vinyl ether, vinyl acetate or saponified 2 products thereof, styrene, vinylpyrolidone, butadiene and so on; copolymers of polyacrylic anhydride, maleic acid, maleic semi-ester, semi-amide and~or derivatives of anhydride or itaconic acid with suitable comonomers such as styrene, ethylene, vinyl ether, vinyl acetate and the like; cellulose derivative or the like.
It is preferable to add ethylenically unsaturated compounds to the photopolymerizable photosensitive composition in order to improve the sensitivity.
' Such compound is a monomer havinq ethylenically unsaturated double bonds which is attacked, when the photopolymerizable photosensitive resin composition is irradiated with actinic light, by the photodecomposed product of the photopolymeriza-tion initiator, and is addition-polymerized three-dimensionally together with the polyfunctional resin and cured, rendering the composition substantially insoluble.
The term "monomer" used herein is intended to mean a concept relative to polymer material and include oligomers such as dimers, trimers and the like, aside from monomers in a strict sense.
The monomers having ethylenically unsaturated double bonds include, for example, unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and - 1~58597 aromatic polyhydroxy compounds, and esters obtained by esterification reaction of unsaturated carboxylic acids, polycarboxylic acids and polyhydroxy compounds such as the above-indicated aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds and the like.
Specific examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.
The aliphatic polyhydroxy compounds include, for example, - 10 dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, propylene glycol, 1,2-butanediol and the like, trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerol and the like, tetrahydric or L5 polyhydric alcohols such as pentaerythritol, tripentaery-thritol and the like, and polyhydroxycarboxylic acids such as dihydroxylmaleic acid and the like.
The aromatic polyhydroxy compounds include hydroquinone, resorcin, catechol, pyrogallol and the like.
Examples of the polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acia, pyromellitic acid, benzophenonedi-carboxylic acid, maleic acid, fumaric acid, malonic acid, glutaric acid, adipic acid, sebacic acid, tetrahydro-phthalic acid, and the like.
1~2S8S9~
Examples of the esters of the aliphatic polyhydroxy compounds ana the unsaturated carboxylic acids are acrylates such as ethylene glycol aiacrylate, triethylene glycol diacrylate, tetramethylene glycol aiacrylate, S trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaery-thritol hexaacrylate, tripentaerythritol octaacrylate, glycerol aiacrylate and the li~e; methacrylates such as - triethylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythr-itol tetraacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, ethylene glycol dimethacrylate, 1,2-butanediol dimethacrylate, sorbitol tetramethacrylate and the like; itaconates such as ethylene glycol diitaconate, propylene glycol diitaconate, 1,2-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol tri- -itaconate and the like; crotonates such as ethylene glycol dicrotonate, diethylene glycol dicrotonate, pentaerythritol tetracrotonate and the like; and malates such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and the like.
The esters of the aromatic polyhydroxy compounds and the unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like.
The esters obtained by the esterification reaction of unsaturated car~oxylic acids, polycarboxylic acids and polyhydroxy compounds are not necessarily a single product.
Typical of the esters are indicated in Table 1. In the table, Z represents an acryloyl or methacryloyl group.
., . - : .
lZ585~7 Table 1 .. . .
z--oC2H4--ooC-c6H4 COO C2H4 ~ 2H4~200C~CH2~4cOO~c2H40~2z Z~C2H4~3OC--CH=CH COO~C2 4 3 ~ 2 4~200C ~ COO~C2H40)2Z
- ' ~
2~ C~ C2H5 C
Z--OCH2 ' CH200C--c6H4--cooc~2~ CH2--Z
Z--OCH2;~ ~ 2 Z
- .CH-OOC-CH=CH-COO-CH ~
Z-OCH2~ 2 Z
z--OC2H4--ooC--c6H4--coo C2H4 Z-OCH2 ~ ~ 2 Z
Z-cH2 /c-cH2ooc-c6H4-coocH2-c -CH20-Z
HO--CH2 . - CH2--OH -Z--OCH2 ~ ~ CH2--Z
10 Z-OCH2--C--CH200C--CH=CH--COOCH2--C--CH20--Z
Z--OC2H4--00C~CH2~4Coo ~CH2 Z--OC2H4--00c~cH2~4CoO--CH
Z--OC2H4--00C~CH2~4Coo CH2 ;~
~'~S~S97 Examples of other compounds having ethylenically - unsaturated double bonds used in the present invention include acrylamides such as acrylamide, ethylene bisacrylamide, hexamethylene bisacrylamide and the like;
methacrylamides such as ethylene bismethacrylamide, hexamethylene bismethacrylamide and the like; allyl esters such as diallyl phthalate, diallyl malonate, diallyl fumarate, triallyl isocyanurate and the like; and vinyl-containing compounds such as divinyl adipate, divinyl phthalate, ethylene glycol dlvinyl ether and the like.
Especially, trimethylolpropane triacrylate; trimethylolethane triacrylate, and pentaerythritol tetraacrylate exhibit relatively high sensitivity and are favorable because they do not lower the ink receptivity on the photocured image areas. - `
The photopolymerization ïnitiators which are another essential component of the composition according to the invention are conventionally known initiators. For - instance, benzoin, benzoin alkyl ethers, benzophenone, anthraquinone, benzil, Michler's ketone, and a mixture of biimidazole and Michler's ketone are favorably used.
In order for effective photosensitization by exposure to visible light of an argon ion laser beam, compounding ; systems such as biimidazole and dialkylaminostyryl derivatives, S-triazine and cyanine derivatives, and S-triazine and thiapyrylium derivatives are preferred.
lZS8597 The composition of the present invention comprises the components in the following ratios ranging 10 - 80 wt~, preferably 20 - 60 wt~ of a polymer containing a poly-functional resin, 90 - 20 wt~, preferably 80 - 40 wt% of an ethylenically unsaturated compound, and 0.1 - 20 wt%, preferably 1 - 10 wt% of a photopolymerization initiator.
The photopolymerizable composition of the invention may be further admixed with other ingredients, depending on the purpose, in order IO modify physical properties. For instance, thermal polymerization inhibitors, antioxidants, colorants, plasticizers, application aids and the ike may:
be compounded in an amount not more than 20 wt~ based on the total weight of the three components.
The photopolymerizable composition of the invention may be used to form a photosensitive material in the absence of solvent, or may be dissolved in a solvent to obtain a solu-tion, followed by applyins it on a support, and drying to form a photosensitive material. The solvents are, for example, methyl ethyl ketone, acetone, cyclohexanone, ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, toluene, xylene, benzene, monochlorobenzene, chloroform, carbon ~etrachloride, trichloroethylene, trichloroethane, dimethylformamide, methyl CELLOSOLVE (trademark), ethyl CELLOSOLVE, butyl CELLOSOLVE, tetrahydrofuran, pentoxone(4-methyl-4-methoxy-2-pentanone), methanol, ethanol, propanol and the like.
`, 4`~ X~
The supports applied for preparing a photosensitive material from the photopolymerizable composition of the invention include, for example, sheets of metals such as aluminium, magnesium, copper, zinc, chromium, nickel, iron S and the like or alloys comprising the metals as a main component, papers such as high quality paper, art paper, release paper and the like, inorganic sheets such as glasses, ceramics and the like, and sheets of polymers such as polyethylene tetrephthalate, polyethylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymers, polystyrene, 6-nylon, 6,6-nylon, cellulose diacetate, cellulose triacetate, cellulose acetate butylate, and the like.
These supports may be ap~lied to a photosensitive layer on both sides of the layer. Moreover, the supports may be treated on the surface thereof in order to control the adhesion strength.
In order to prevent the photopolymerizable composition of the present invention from suffering disadvantageous effects of oxygen such as lowered sensitivity, deteriora-tion of storage stability and the like, any known techniques may be used, for example, a releasable transparent cover sheet may be provided on the photosensitive layer, or a covering layer of, for example, a wax material or a water-soluble or an alkali-soluble polymer may be formed on the layer.
12S859~7 The light sources for exposure suitably applicable to the composition of the present invention include general-purpose light source capable of emitting ultraviolet and visible light rays having wavelengths over 180 nm such as, for example, high pressure mercury lamps, xenone lamps, metal halide lamps, fluorescent lamps, tungsten lamps, argon ion laser, helium cadmium laser, krypton laser and the like.
The photopolymerizable composition of the present invention has uses in various fields of, for example, making of printing plates for lithograph, intaglio, and relief printing or the li~e, photoresists for the preparation of :
printed circuits or IC circuits, dry films, non-silver halide lith films, and image formation of relief images and reproduction of images. Having generally described the lS invention, a more complete understanding can be obtained by-refexence to certain specific examples, which are included for purposes of illustration only and are not intended to be limiting unless otherwise specified.
Reference 1 9.0 g of methyl methacrylate, 0.86 g of methacrylic acid (charging ratio by mole = 9/1), and 50 mg of benzoyl peroxide were dissolved in 50 g of dioxane, followed by heating the solution at 80C for 4 hours with agitation while purging with nitrogen and subsequently charging into a large amount of water. The resulting polymer was dissolved in a small amount of acetone and dropped into a - large amount of a methanol/water mixture for re-precipita-i~58597 tion, followed by drying in vacuo to obtain methyl meth-acrylate/methacrylic acid copolymer (molecular weight ~
;, 000) Reference 2 8.08 g (0.01 mole) of a partially esterified product of styrene-maleic anhydride copolymer (styrite C~-2L, molecular weight ~ 5vO00/product by Sankyo Kasei Co., Ltd.), 2.32 g (0.02 mole) of 2-hydroxyethyl acrylate, and 20 mg of hydroquinone were dissolved in 50 g of dioxane, followed by heating at 100C for 4 hours under agitation and dropping in a large amount of water for precipitation. Thereafter, the precipitate was dried in vacuo to obtain a carboxylic acid semi-ester polymer (monofunctional resin).
Re~erence 3 The procedure of Reference 2 was repeated except that pentaerythritol triacryla~e was used instead of 2-hydro-xyethyl acrylate, there~y obtaining a carooxylic semi-ester polymer (polyfunctional resin).
Reference 4 The procedure of Reference 2 was repeated except that trimethylolethane diacrylate was used instead of 2-- - hydroxyethyl acrylate, therehy obtaining a carboxylic acid semi-ester polymer (polyfunctional resin).
Example 1 0.45 g of a partially esterified product of styrene/maleic anhydride copolymer (STYRITE CM-2L, trademark, product of Sankyo Kasei l'~S859~7 Co., Ltd.), 0.1 g of the methyl methacrylate/methacrylic acid copolymer prepared in Reference 3, 0.45 g of the polyfunctional resin of reference 3, 0.5 g of trimethylol-propane triacrylate (product of Osaka Organic Chem. Ind.
Co., Ltd.), each 0.04 g of photopolymerization initiators represented ~y the following structural formulas ~I] and [II~, and 0.012 g of "~ictoria Pure Blue BOH" (product of ~odogaya Chemical Co., Ltd.)-were dissolved in 18 g of ethyl cellosolve. The resulting photosensitive solution was applied onto a grained and anodized al~minium plate by the use of a whirler in a dry thickness of 20 mg/dm2. At this stage no stic~ness was observed on the photosensitive layer. Thereafter, an aqueous polyvinyl alcohol solution was applied onto the photosensitive layer to form a protective layer with a dry thickness of 20 mg/dm2, thereby o~taining a sample A step tablet (by Eastman Kodak Co.) was deposited on the sample under vacuum, followed by expos-ing it to light from a 3 KW high pressure mercury lamp (U~IPULSE UMH-3000, trademark, by Ushio Electric Inc.) at a distance of 1 m for 15 seconds and developing with a liquid developer consisting of an aqueous 1% sodium silicate solu-tion. As a result, the sensitivity (steps of photocured image) was found to be 12 steps. Furthermore, the developa-bility (developing speed, removability by dissolution, and the like), resolution and ink receptivity were found to be good. Thus, the fundamental requirements as the offset PS
plate were satisfied.
i~
125~37 - ~4 -
3 ~ ~ C13 N~ N .................... [I]
O
~ >=C < ~ ............................. ~IIJ
Comparative Example l The general procedure of Example l was repeated except that the same amount of the monofunctional resin obtained in Reference 2 was used instead of the polyfunctional polymer, thereby obtaining a sample. The sample was evaluated in the same manner as in Exampie l, revealing the sensiliviiy or steps, which was as low 2S l/4 time the sensitivity of Example l.
Example 2 The general procedure or Exc~Le I ~s repeated exce?t tn-.
the trimethylolpropane triacrylate was increased in amount from 0.5 g to l.O g, thereby obtaining a sample. The sample was evaluated in the same manner as in Example l, revealing that the sensitivity of 14 steps.
.. .
` iZS8597 Example 3 The general procedure of Example 1 was repeated except that the trimethylolpropane triacrylate was removed from the photosensitive solution, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, revealing that the sensitivity of 5 steps.
Comparative Example 2 The general procedure of Example 1 was repeated except that the trimethylolpropane triacrylate was removed from the photosensitive solution of Comparative Example 1, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, with the result that no photocured image was formed and even when the exposure time was extended to 150 seconds which was ten times longer, no photocured image was observed.
Example 4 The general procedure of Example 1 was repeated except that the polyfunctional resin prepared in Reference 4 was used instead of the polyfunctional resin obtained in Reference 3, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, revealing the sensitivity of 10 steps, which was an high as 2 times the sensitivity of the sample using the monofunctional resin described in Comparative Example 1.
l'~S8S~7 Example 5 0.4 g of a partially esterified product of styrene/maleic anhydride copolymer (Styrite CM-2L, product by Sankyo Kasei Co., Ltd.), ~ 1 g of the methyl methacrylate/methacrylic acid copolymer obtained in Reference 1, 0.5 g of the polyfunctional resin obtained in Reference 3,0.1 g of dioctyl phthalate,l.0 g of trimethylolpropane triacrylate (product of Osaka Organic Chem. Ind. Co., Ltd.), 0.1 g of 2,2'-bis(orthobromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 0.05 g of 2-(paradiethylaminostyryl)-benzo[4,5]benzothiazole, 0.06 g of Z-mercaptobenzothlazole, and 0.012 g of "Victoria Pure Blue BOH" (product of Hodogay~ Chemical Co., Ltd.)~w~Ee dissolved in 18 g of ethyl cellosolve to obtain a photo-sensitive solution. The solution was applied onto a grained and anodized aluminium plate by the use of a whirler in a dry thic~néss of 20 my/dm2. Thereafter, an aqueous polyvinyl alcohol solution was applied onto the layer to form a protective layer with a dry thickness of 20 mg/dm2, thereby obtaining a sample. The sample was exposed to a visible light beam with a wavelength of 488 nm from an argon ion laser irradiator (Gas Laser GLG-3300, by Nippon Electric Co., Ltd.) under conditions of an irradiation beam diameter on the plate of 15 microns and a light quantity of 10 mW for different scanning speeds up to 55 m/sec. Thereafter, the irradiated sample was developed with a liquid developer consisting of an aqueous 1% sodium silicate solution. As a result, it was found that an irradiation energy necessary if~5859~ .
for obtained a photocured image capable of faithfully reproducing the irradiation beam diameter was found to be 1 - 3 mJ/cm2.
Example 6
O
~ >=C < ~ ............................. ~IIJ
Comparative Example l The general procedure of Example l was repeated except that the same amount of the monofunctional resin obtained in Reference 2 was used instead of the polyfunctional polymer, thereby obtaining a sample. The sample was evaluated in the same manner as in Exampie l, revealing the sensiliviiy or steps, which was as low 2S l/4 time the sensitivity of Example l.
Example 2 The general procedure or Exc~Le I ~s repeated exce?t tn-.
the trimethylolpropane triacrylate was increased in amount from 0.5 g to l.O g, thereby obtaining a sample. The sample was evaluated in the same manner as in Example l, revealing that the sensitivity of 14 steps.
.. .
` iZS8597 Example 3 The general procedure of Example 1 was repeated except that the trimethylolpropane triacrylate was removed from the photosensitive solution, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, revealing that the sensitivity of 5 steps.
Comparative Example 2 The general procedure of Example 1 was repeated except that the trimethylolpropane triacrylate was removed from the photosensitive solution of Comparative Example 1, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, with the result that no photocured image was formed and even when the exposure time was extended to 150 seconds which was ten times longer, no photocured image was observed.
Example 4 The general procedure of Example 1 was repeated except that the polyfunctional resin prepared in Reference 4 was used instead of the polyfunctional resin obtained in Reference 3, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, revealing the sensitivity of 10 steps, which was an high as 2 times the sensitivity of the sample using the monofunctional resin described in Comparative Example 1.
l'~S8S~7 Example 5 0.4 g of a partially esterified product of styrene/maleic anhydride copolymer (Styrite CM-2L, product by Sankyo Kasei Co., Ltd.), ~ 1 g of the methyl methacrylate/methacrylic acid copolymer obtained in Reference 1, 0.5 g of the polyfunctional resin obtained in Reference 3,0.1 g of dioctyl phthalate,l.0 g of trimethylolpropane triacrylate (product of Osaka Organic Chem. Ind. Co., Ltd.), 0.1 g of 2,2'-bis(orthobromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 0.05 g of 2-(paradiethylaminostyryl)-benzo[4,5]benzothiazole, 0.06 g of Z-mercaptobenzothlazole, and 0.012 g of "Victoria Pure Blue BOH" (product of Hodogay~ Chemical Co., Ltd.)~w~Ee dissolved in 18 g of ethyl cellosolve to obtain a photo-sensitive solution. The solution was applied onto a grained and anodized aluminium plate by the use of a whirler in a dry thic~néss of 20 my/dm2. Thereafter, an aqueous polyvinyl alcohol solution was applied onto the layer to form a protective layer with a dry thickness of 20 mg/dm2, thereby obtaining a sample. The sample was exposed to a visible light beam with a wavelength of 488 nm from an argon ion laser irradiator (Gas Laser GLG-3300, by Nippon Electric Co., Ltd.) under conditions of an irradiation beam diameter on the plate of 15 microns and a light quantity of 10 mW for different scanning speeds up to 55 m/sec. Thereafter, the irradiated sample was developed with a liquid developer consisting of an aqueous 1% sodium silicate solution. As a result, it was found that an irradiation energy necessary if~5859~ .
for obtained a photocured image capable of faithfully reproducing the irradiation beam diameter was found to be 1 - 3 mJ/cm2.
Example 6
4.6 g of glycerine was dissolved in 50 g of ethyl acetate, to which several drops of triethylamine was added while agitating. Thereafter, a 1,4-dioxane solution of 10 g of acrylic chloride was dropped into the solution, followed by agitating at room temperature for further 2 hours and further agitating for 1 hour after raising the temperature up to 50C. The reaction solution was discharged and admixed with water, followed ~y shaking, removing water-soluble components from the system and distilling off the 1,4-dioxane to obtain glycerol-1,3-diacrylate. 10 g (0.05 mole) of the glycerol-1,3-diacrylate, 20.2 g (0.03 mole) of a partially esterified product of styrene/maleic anhydride copolymer ("Styrite CM-2L", molecular weight ~ 5000, product of Sankyo Kasei Co., Ltd.), 20 mg of hydroquinone were dissolved in 85 g of 1,4-dioxane and agitated at 90C for 4 hours, followed ~y dropping the reaction solution into 3 - liters of water and drying the resulting precipitate in vacuo, thereby obtaining a carboxylic acid semi-ester polymer (polyfunctional resin).
0.45 g of the polyfunctional resin obtained by adding the glycerol-1,3-diacrylate in the side chains thereof, 0.45 g of a partially esterified product of styrene~maleic anhydride lZ58597 copolymer (CM-2L~, and 0.1 g of the methyl methacrylate/
methacrylic acid copolymer obtained in Reference 1 were dissolved in ethyl cellosolve together with the ethylenically unsaturated compound, photopolymerization initiator and dye used in Example 1 in the same manner as in Example 1, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, with the result that the sensitivity was found to be 10 steps.
~aving now fully described this invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
0.45 g of the polyfunctional resin obtained by adding the glycerol-1,3-diacrylate in the side chains thereof, 0.45 g of a partially esterified product of styrene~maleic anhydride lZ58597 copolymer (CM-2L~, and 0.1 g of the methyl methacrylate/
methacrylic acid copolymer obtained in Reference 1 were dissolved in ethyl cellosolve together with the ethylenically unsaturated compound, photopolymerization initiator and dye used in Example 1 in the same manner as in Example 1, thereby obtaining a sample. The sample was evaluated in the same manner as in Example 1, with the result that the sensitivity was found to be 10 steps.
~aving now fully described this invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
Claims (6)
1. A photopolymerizable photosensitive composition characterized by comprising a photopolymerizable photo-sensitive resin having polyfunctional ethylenically unsaturated groups in the side chains or end groups thereof, and a photopolymerization initiator.
2. A photopolymerizable photosensitive composition accord-ing to Claim 1, wherein said polyfunctional ethylenically unsaturated groups have structural units of the general formula (in which Rl represents hydrogen atom, an alkyl group or a hydroxyalkyl group, R2 represents an alkylene group, R3 represents hydrogen atom or methyl group and m is O
or 1 and n is 2 or 3 provided that m + n = 3, and p is an integer of 1 to 3).
or 1 and n is 2 or 3 provided that m + n = 3, and p is an integer of 1 to 3).
3. A photopolymerizable photosensitive composition accord-ing to Claim 2 wherein R2 is methylene group and p is 1.
4. A photopolymerlzable photosensitive composition accord-ing to Claim 1, wherein said photopolymerizable photo-sensitive resin comprises units of the general formula (in which Rl represents hydrogen atom, an alkyl group or a hydroxyalkyl group, R2 represents an alkylene group, R3 and R4 independently represent hydrogen atom or methyl group, R represents hydrogen atom or carboxyl group, m is O or 1 and n is 2 or 3 provided that m + n = 3, p is an integer of 1 to 3, and q is an integer of O to 3).
5. A photopolymerizable photosensitive composition accord-ing to Claim 4 wherein R is methylene group and p is 1.
.
.
6. A photopolymerizable photosensitive composition accord-ing to Claim 1, further comprising an ethylenically unsaturated compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57182471A JPS5971048A (en) | 1982-10-18 | 1982-10-18 | Photopolymerizable photosensitive composition |
| JP182471/1982 | 1982-10-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258597A true CA1258597A (en) | 1989-08-22 |
Family
ID=16118839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000438783A Expired CA1258597A (en) | 1982-10-18 | 1983-10-12 | Photopolymerizable photosensitive composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4537855A (en) |
| EP (1) | EP0106351B2 (en) |
| JP (1) | JPS5971048A (en) |
| AU (1) | AU553478B2 (en) |
| CA (1) | CA1258597A (en) |
| DE (1) | DE3373221D1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3448089A (en) * | 1966-03-14 | 1969-06-03 | Du Pont | Photopolymerizable polymers containing free acid or acid anhydride groups reacted with glycidyl acrylate or glycidyl methacrylate |
| US3871885A (en) * | 1971-05-18 | 1975-03-18 | Du Pont | Crystalline photo-polymerizable composition |
| JPS5018401B1 (en) * | 1971-06-23 | 1975-06-28 | ||
| JPS5034444B2 (en) * | 1971-08-20 | 1975-11-08 | ||
| US3900594A (en) * | 1971-12-17 | 1975-08-19 | Grace W R & Co | Photocurable triazine containing polyene-polythiol lacquer composition |
| IT977259B (en) * | 1972-02-09 | 1974-09-10 | Minnesota Mining & Mfg | PHOTORETICULATING POLYMER COM POSITION CONTAINING SUCH POLYMER AND PROCEDURE FOR COATING SURFACES WITH SAID COMPOSITION |
| DE2406400B2 (en) * | 1973-02-14 | 1977-04-28 | Hitachi Chemical Co., Ltd., Tokio | LIGHT-SENSITIVE RESIN COMPOSITIONS ON THE BASIS OF COMPOUNDS WITH EPOXY OR. PHOTOPOLYMERIZABLE ACRYLIC GROUPS |
| US4060656A (en) * | 1973-04-02 | 1977-11-29 | Teijin Limited | Support for photosensitive resin |
| DE2361041C3 (en) * | 1973-12-07 | 1980-08-14 | Hoechst Ag, 6000 Frankfurt | Photopolymerizable mixture |
| JPS5179342A (en) * | 1974-12-26 | 1976-07-10 | Fuji Photo Film Co Ltd | |
| JPS5397416A (en) * | 1977-02-04 | 1978-08-25 | Asahi Chemical Ind | Light polymeric constitute possible for water development |
| JPS54129044A (en) * | 1978-03-31 | 1979-10-06 | Ube Ind Ltd | Photo-setting resin composition |
| JPS5550001A (en) * | 1978-10-06 | 1980-04-11 | Fuji Photo Film Co Ltd | Photo-polymerizable composition |
| CA1138375A (en) * | 1978-11-01 | 1982-12-28 | James E. Moore | Photocurable acrylic coated polycarbonate articles |
| JPS5575405A (en) * | 1978-11-30 | 1980-06-06 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| DE3048502A1 (en) * | 1980-12-22 | 1982-07-22 | Hoechst Ag, 6000 Frankfurt | POLYMERIZABLE MIXTURE BY RADIATION AND RADIATION-SENSITIVE RECORDING MATERIAL MADE THEREOF |
| JPS57165422A (en) * | 1981-04-07 | 1982-10-12 | Asahi Chem Ind Co Ltd | Urethane prepolymer |
-
1982
- 1982-10-18 JP JP57182471A patent/JPS5971048A/en active Granted
-
1983
- 1983-09-29 AU AU19733/83A patent/AU553478B2/en not_active Ceased
- 1983-10-11 US US06/540,868 patent/US4537855A/en not_active Expired - Lifetime
- 1983-10-12 CA CA000438783A patent/CA1258597A/en not_active Expired
- 1983-10-17 DE DE8383110346T patent/DE3373221D1/en not_active Expired
- 1983-10-17 EP EP83110346A patent/EP0106351B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5971048A (en) | 1984-04-21 |
| EP0106351A3 (en) | 1984-09-12 |
| EP0106351B1 (en) | 1987-08-26 |
| US4537855A (en) | 1985-08-27 |
| AU1973383A (en) | 1984-05-03 |
| AU553478B2 (en) | 1986-07-17 |
| EP0106351B2 (en) | 1991-10-09 |
| DE3373221D1 (en) | 1987-10-01 |
| JPH0469381B2 (en) | 1992-11-06 |
| EP0106351A2 (en) | 1984-04-25 |
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